CN103011285B - Process for producing pentahydrate bismuth nitrate by employing crude bismuth oxide - Google Patents
Process for producing pentahydrate bismuth nitrate by employing crude bismuth oxide Download PDFInfo
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- CN103011285B CN103011285B CN201210577194.2A CN201210577194A CN103011285B CN 103011285 B CN103011285 B CN 103011285B CN 201210577194 A CN201210577194 A CN 201210577194A CN 103011285 B CN103011285 B CN 103011285B
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Abstract
The invention relates to a process for producing pentahydrate bismuth nitrate by employing crude bismuth oxide. The process comprises the following steps of: adding nitric acid to remove chemical impurities, and preparing a novel compound containing a nitric acid insoluble substance; removing the nitric acid insoluble substance, crystallizing the acid-soluble filtrate through evaporation and concentration, thereby obtaining a pentahydrate bismuth nitrate crystal and a bismuth nitrate mother solution. The pentahydrate bismuth nitrate product is prepared by performing deep processing on the crude bismuth oxide by using the process, and compared with the pyrogenic attack, the precursor preparing and calcining is saved; the consumption of chemical reagents is low, the cost is only about 1/2, and compared with other wet process treatment, lots of chemical reagent auxiliary materials are saved, the process flow is shortened, and the cost is greatly reduced; and meanwhile, the treatment cost of wastewater and waste gas is reduced, and the process is environment-friendly.
Description
Technical field
The present invention relates to a kind of production method of bismuth-series chemical product, especially relate to the technique that the thick bismuth oxide of a kind of use is produced five water Bismuth trinitrates.
Background technology
The raw material of producing five water Bismuth trinitrate Chemicals generally has 2 kinds, and one is smart bismuth, first prepares bismuth oxide by smart bismuth, then makes Bismuth trinitrate, finally makes the bismuth-series chemical products such as five water Bismuth trinitrates.Such as on January 20th, 2010, Chinese invention patent application publication number CNl01628735A, the preparation method of disclosed a kind of bismuth-series chemical product.The method requires high to raw materials for production essence bismuth, cause production cost high.Another kind is directly to make Bismuth trinitrate with bismuth oxide, also can make the bismuth-series chemical products such as five water Bismuth trinitrates.But desired bismuth oxide purity is quite high, and the bismuth oxide of my company comes from a kind of electric arc furnace settling pocket material, impure many.Main manifestations for contain Pb, Cu,, the impurity atom such as As, Na, Ag, Fe, Ni, Ca, K, Si, Sb, also contain the carbon class physical impurity that is insoluble to nitric acid.In this class bismuth oxide industry, be called as thick bismuth oxide.Obviously, this thick bismuth oxide can not reach the bismuth oxide raw material use standard of producing.Conventional process pattern adopts returns smeltery by this thick bismuth oxide, and fire reduction, removal of impurities, ingot casting essence bismuth re-use again; Also having the means of processing is to make its hydrometallurgy fully dissolving by employing acid adding, filters physical impurity, by crystallization, adds alkali and prepares new compound or pass through extracting and separating.Any method all exists processing cost too high above, will consume a large amount of chemical reagent and discharge a large amount of waste water.
Summary of the invention
Order of the present invention is the problem for described existence, and a kind of use technique that thick bismuth oxide is produced five water Bismuth trinitrates is provided, and solves the problem that traditional technology will consume a large amount of chemical reagent and discharge a large amount of waste water simultaneously.Production cost is significantly reduced, and technical process is brief.
Solution of the present invention is: the technique that the thick bismuth oxide of a kind of use is produced five water Bismuth trinitrates, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb7-12, Cu 25-30, As 1.5-3, Na 0.5-3, Ag 4-7, Fe 100-125, Ni 1-3, Ca 500-600, K 1-4, Si 60-70, Sb 3-5, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take thick bismuth oxide-60 order >=95% that sieve, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; Take gram/gram as unit, liquid-solid mass ratio is 2-20: 1; Nitric acid and thick bismuth oxide raw materials quality are than 1-1.5: 1, temperature of reaction 0-200 ℃ (preferably 85 ℃), reaction times 1-48h (preferably 4 hours) carries out chemical subtraction, controls supernatant liquor pH0.5-1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5-5: 1, and temperature 0-100 ℃; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Above-mentioned thick bismuth oxide raw material comes from a kind of electric arc furnace settling pocket material.
Above-mentioned new compound is mainly bismuth subnitrate.
The above-mentioned carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
The main component of above-mentioned acid-soluble filtrate is Bismuth trinitrate.
Innovative point of the present invention has been to have broken in processing step the conventional thinking of utilizing nitric acid to remove to dissolve bismuth, in thick bismuth oxide raw material, add conditionally nitric acid dissolve contain Pb, Cu,, the impurity atom such as As, Na, Ag, Fe, Ni, Ca, K, Si, Sb.The present invention break through key problem in technology be, utilize reaction conditions control nitric acid, allow bismuth generate a kind of bismuth subnitrate compound of insoluble in water, make impurity atom become filtrate and separate with bismuth.
The present invention has positive economic benefit and social benefit, and economic benefit shows:
Adopt deep processing of the present invention to prepare five water Bismuth trinitrate crystal products, compare pyrogenic attack and do again five water Bismuth trinitrate crystal products, omitted presoma preparation and calcination; Chemical reagent consumption is few, and cost is only 1/2 left and right, compares other wet processings, has also saved a large amount of chemical reagent auxiliary materials, brief technical process, and cost has also obtained reducing greatly; Compare equally the discharge that CNl01628735A technique also greatly reduces waste water, waste gas, reduced waste water, off gas treatment cost simultaneously, environment is more friendly.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Also describe by reference to the accompanying drawings the present invention in detail by embodiment below.
Embodiment 1
The technique that the thick bismuth oxide of use is produced five water Bismuth trinitrates, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 9, Cu 30, As 1.5, Na 3, Ag 4, Fe 100, Ni 3, Ca 500, K 2, Si 70, Sb 5, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take thick bismuth oxide 50g 96% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 50g; Take gram/gram as unit, liquid-solid mass ratio is 2: 1; Nitric acid with thick bismuth oxide raw materials quality than 1: 1,85 ℃ of temperature of reaction, 4 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH0.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 1: 1,85 ℃ of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 3, K-, Si 2, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 2
The technique that the thick bismuth oxide of use is produced five water Bismuth trinitrates, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 7, Cu 28, As 2, Na 0.5, Ag 6, Fe 125, Ni 2, Ca 560, K 3, Si 64, Sb 3, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take thick bismuth oxide 50g 98% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; Take gram/gram as unit, liquid-solid mass ratio is 20: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,0 ℃ of temperature of reaction, 48 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH1; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 5: 1, temperature 50 C; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 4, K-, Si 2, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 3
The technique that the thick bismuth oxide of use is produced five water Bismuth trinitrates, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 10, Cu 25, As 3, Na 3, Ag 7, Fe 110, Ni 3, Ca 540, K 1, Si 60, Sb 4, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take thick bismuth oxide 50g-60 orders that sieve and account for 95% of total mass, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 60g; Take gram/gram as unit, liquid-solid mass ratio is 4: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.2: 1,200 ℃ of temperature of reaction, 1 hour reaction times was carried out chemical subtraction, controlled supernatant liquor pH1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5: 1,100 ℃ of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 3, K-, Si 3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 4
The technique that the thick bismuth oxide of use is produced five water Bismuth trinitrates, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 12, Cu 26, As 2, Na 0.5, Ag 5, Fe 117, Ni 1, Ca 600, K 4, Si 65, Sb 4, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take thick bismuth oxide 50g 97% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; Take gram/gram as unit, liquid-solid mass ratio is 10: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,100 ℃ of temperature of reaction, 24 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 4: 1,0 ℃ of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 4, K-, Si 3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Claims (4)
1. produce a technique for five water Bismuth trinitrates with thick bismuth oxide, in the thick bismuth oxide raw material of use, contain impurity atom as follows by PPM densitometer: Pb7-12, Cu 25-30, As 1.5-3, Na 0.5-3, Ag 4-7, Fe 100-125, Ni 1-3, Ca 500-600, K 1-4, Si 60-70, Sb 3-5, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; It is characterized in that: concrete technology step is as follows:
1. take thick bismuth oxide-60 order >=95% that sieve, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; Take gram/gram as unit, liquid-solid mass ratio is 2-20: 1; Nitric acid and thick bismuth oxide raw materials quality are than 1-1.5: 1, and temperature of reaction 0-200 ℃, reaction times 1-48h carries out chemical subtraction, controls supernatant liquor pH0.5-1.5; Be prepared into a kind of bismuth subnitrate compound; Make the mass percent of bi content in compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5-5: 1, and temperature 0-100 ℃; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate, by evaporating, concentrating and crystallizing, obtains five water Bismuth trinitrate crystal and Bismuth trinitrate mother liquor; It is as follows that this five water Bismuth trinitrate crystal chemistry impurity is pressed PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
2. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced five water Bismuth trinitrates, is further characterized in that: described thick bismuth oxide raw material comes from a kind of electric arc furnace settling pocket material.
3. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced five water Bismuth trinitrates, is further characterized in that: the described carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
4. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced five water Bismuth trinitrates, is further characterized in that: the main component of described acid-soluble filtrate is Bismuth trinitrate.
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| GB881810A (en) * | 1958-10-28 | 1961-11-08 | Karl Jonard | Compound basic bismuth nitrate and method of manufacturing the same |
| JP2949227B1 (en) * | 1998-06-30 | 1999-09-13 | 科学技術庁無機材質研究所長 | Hydrous bismuth compounds with excellent inorganic anion exchange properties and their production |
| CN100528758C (en) * | 2007-03-28 | 2009-08-19 | 湖南金旺实业有限公司 | Method for producing powder in micron order of bismuth oxide |
| CN101628735B (en) * | 2009-08-24 | 2011-11-16 | 长沙金堂铋业有限公司 | Method for preparing bismuth-series chemical product |
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